This invention relates to a hair cosmetic composition comprising (a) an amine-oxide-containing copolymer and (b) a water-soluble polymer selected from nonionic, cationic, anionic and amphoteric polymers. The composition of the present invention has an excellent hair setting property, and imparts good flexibility and a good finish feeling so that it is useful for applications such as a hair spray, hair mousse, hair setting lotion and hair gel.
In order to retain hair in a desired shape, it is a common practice to set hair by applying thereto a solution of a film-forming polymer compound in water or a lower alcohol, or a mixed solvent thereof, and then drying.
Nonionic high-molecular compounds such as polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate copolymer are widely used as the film-forming polymer compounds. Such PVP and PVP/VA copolymers are described in the International Cosmetic Ingredient Dictionary published by The Cosmetic, Toiletry, and Fragrance Association, JP-B-46-19637 (the term xe2x80x9cJP-Bxe2x80x9d as used herein means an xe2x80x9cexamined published Japanese patent publicationxe2x80x9d) and JP-A-51-144480 (the term xe2x80x9cJP-Axe2x80x9d as used herein means an xe2x80x9cunexamined published Japanese patent application). However, the use of these compounds is accompanied by the following drawbacks. In order to bring about high hair setting effects, the film formed therefrom is hard and lacks flexibility. This stiffens the hair, and under highly humid conditions causes hair to stick. Thus, the subject compounds do not have sufficient hair setting effects. Use of the above compounds is also accompanied by flaking. That is, a phenomenon where the film thus formed is divided into small flakes by combing after hair setting. Also, due to static charge, the hair spreads and cannot be easily set. Judging from these points, the above-exemplified compounds are unsatisfactory.
The use of anionic polymer compounds as the film-forming polymer compounds is also known. However, the film formed therefrom is hard as a result of increasing the hair setting effects, it stiffens the hair due to lack of flexibility, and the resulting hair setting effects are not satisfactory. In addition, its use is accompanied by flaking, and due to static charge, the hair spreads and cannot easily be set. From these points, the anionic polymer compounds are therefore unsatisfactory. To overcome such problems, there has been an attempt to add a cosmetic additive such as oils and fats or a surfactant. However, this brings about further deterioration in the hair setting effects. Thus, a hair cosmetic composition having a well-balanced performance has not yet been prepared using an anionic polymer compound.
Cationic polymer compounds have also been widely used as the film-forming polymer compound to retain the desired hair shape and to improve the touch feeling upon application of the resulting composition. These compounds, however, are disadvantageous in that they do not have sufficient hair setting effects to retain the desired hair shape, and due to the flexibility of the film thus formed, hair having a retained shape lacks resilience particularly under high humidity conditions. Moreover, when the hair cosmetic composition containing a cationic polymer compound is used repeatedly, the cationic polymer compound accumulates on the hair. This causes build-up problems such as deterioration in the combing property or appearance of the hair. Thus, the cationic polymer compound is unsatisfactory as the film-forming compound.
Amphoteric polymer compounds have also come to be widely used as the film-forming polymer compound (JP-A-49-14647, JP-A-51-9732, JP-A-55-104209, etc.). These compounds are unsatisfactory because they stiffen the hair due to lack of flexibility, are unable to retain the desired shape of the hair particularly under high-humidity conditions and therefore do not provide sufficient hair setting effects, and cannot be sufficiently removed by washing. Thus, the amphoteric polymer compounds are also unsatisfactory as the film-forming compound.
To overcome the above-described problems, particularly, to improve hair setting effects and resilience, JP-A-55-59107 proposes a hair cosmetic composition comprising a cationic polymer compound and an anionic polymer, while JP-A-58-124712 proposes a hair cosmetic composition comprising a cationic polymer compound and an amphoteric polymer.
Even the above compositions do not provide satisfactory performance as a hair setting composition in terms of hair setting effects or resilience.
It is therefore an object of the present invention to provide a hair setting cosmetic composition which overcomes the above-described problems of conventional film-forming polymers such as cationic polymers, anionic polymers, nonionic polymers or amphoteric polymers, which has an excellent hair setting property, and which imparts to hair good resilience and a good finish feeling.
The present inventors found that the above objectives can be obtained by using, as film-forming polymer compounds, a conventional water-soluble polymer compound having a weight-average molecular weight of 5,000 to 500,000 in combination with a novel water-soluble amine-oxide-containing polymer compound, to thereby achieve the present invention.
Thus, the present invention provides a hair cosmetic composition comprising (a) a water-soluble amine-oxide-containing polymer having a weight-average molecular weight of 10,000 to 500,000 and (b) a water-soluble polymer selected from the group consisting of nonionic polymers, cationic polymers, anionic polymers and amphoteric polymers, the weight ratio of said component (a) to said component (b) falling within a range of from 1:10 to 10:1 and said components (a) and (b) being incorporated in a total amount of from 0.1 to 10 wt. % based on the hair cosmetic composition.
In the present invention, the term xe2x80x9cwater solubilityxe2x80x9d as used herein means as follows: when an aqueous solution obtained by stirring 1 part by weight of an amine-oxide-containing resin and 99 parts by weight of a deionized water under heat at 60xc2x0 C. for two hours is uniform even after cooling and being allowed to stand for one day at room temperature; and has, in a 1 cmxc3x971 cm cell, a transmittance of 70% or greater at 655 nm, it is regarded to have water solubility.
The amine-oxide-containing polymer for use as component (a) in the present invention has (a1) a polymer structure composed of an amine-oxide-containing unsaturated monomer or has (a2) a polymer structure composed of an amine-oxide-containing unsaturated monomer and a hydrophobic unsaturated monomer. A copolymer structure composed of 15 to 90 wt. % of an amine-oxide-containing monomer and 85 to 10 wt. % of a hydrophobic monomer is preferred.
The term xe2x80x9cthe component (a1) having a polymer structure composed of an amine-oxide-containing unsaturated monomerxe2x80x9d as used herein includes a polymer which is prepared by any one of the processes (1) to (4) described below, to thereby obtain a polymer comprising structural units containing an amine-oxide group.
Among the processes described below, (2) is preferred for preparing the amine-oxide-containing polymer (a1).
(1) A process of polymerizing an amine-oxide-containing monomer (A) obtained by forming an oxide of a nitrogen-containing monomer.
(2) A process of polymerizing a nitrogen-containing monomer, followed by forming an oxide of the nitrogen-containing group.
(3) A process of polymerizing a monomer having a reaction-active functional group, followed by reacting with a substance containing both a group reactive with the functional group and an amine-oxide group.
(4) A process of polymerizing a monomer having a reaction-active functional group, followed by reacting with a substance containing both a group reactive with the functional group and a nitrogen-containing group, and then forming an oxide of the nitrogen-containing group.
The term xe2x80x9cthe component (a2) having a copolymer structure composed of an amine-oxide-containing unsaturated monomer and a hydrophobic unsaturated monomerxe2x80x9d as used herein includes a polymer which is prepared by any one of processes (5) to (8) described below, to thereby obtain a polymer containing structural units derived from a monomer containing an amine-oxide group and a hydrophobic unsaturated monomer.
Among these processes, (6) is preferred for preparing the amine-oxide-containing polymer (a2).
(5) A process of copolymerizing an amine-oxide-containing monomer (A) obtained by forming an oxide of a nitrogen-containing monomer, and a hydrophobic unsaturated monomer (B).
(6) A process of copolymerizing a nitrogen-containing unsaturated monomer and a hydrophobic unsaturated monomer (B), followed by forming an oxide of the nitrogen-containing group.
(7) A process of copolymerizing a monomer having a reaction-active functional group and a hydrophobic unsaturated monomer (B), followed by reacting with a substance having both a group reactive with the functional group and an amine oxide group.
(8) A process of copolymerizing a monomer having a reaction-active functional group and a hydrophobic unsaturated monomer (B), followed by reacting with a substance having both a group reactive with the functional group and a nitrogen-containing group and then forming an oxide of the nitrogen-containing group. Amine-oxide-containing monomer (A):
Examples of the amine-oxide-containing monomer as component (A) include monomers represented by the following formulas (I) to (IV): 
wherein R1 represents a hydrogen atom or a methyl group, R2 and R3 are the same or different and each independently represents a C1-24 alkyl group C6-24 aryl group or C7-24 arylalkyl group, R4 and R5 each independently represents a C1-24 alkyl group, C6-24 aryl group or C7-24 arylalkyl group, X represents a divalent linking group, m is 0 or 1, n is an integer of 0 to 4 and p is an integer of 0 to 3, Y represents 
in which at least one of R6to R13 represents 
and the other of R6 to R13 each represents a hydrogen atom, C1-24 alkyl group, C6-24 aryl group or C7-24 arylalkyl group, and a and b are the same or different and each independently represents an integer of 1 to 10.
Examples of the monomer represented by formula (I) include amine-oxide-introduced products obtained by forming the oxide of the nitrogen atom of N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate (which is hereinafter abbreviated as N,N-dimethylaminoethyl (meth)acrylate), N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, vinyl N,N-dimethylaminorpropionate, p-dimethylaminomethylstyrene, p-dimethylaminoethylstyrene, p-diethylaminomethylstyrene and p-diethylaminoethylstyrene; amine-oxide introduced products obtained by forming the oxide of the nitrogen atom of the reaction product between an unsaturated-containing acid anhydride such as maleic anhydride, itaconic anhydride or crotonic anhydride and N,N-dimethyl-1,3-propaneamine or N,N-dimethyl-p-phenylenediamine having both a group reactive with the acid anhydride group and a tertiary amino group; and amine-oxide-introduced products obtained by forming the oxide of the nitrogen atom of the reaction product between an epoxy-containing monomer such as glycidyl methacrylate and a compound such as N,N-dimethyl-1,3-propaneamine or N,N-dimethyl-p-phenylenediamine having both a group reactive with the epoxy group and a tertiary amino group. Examples also include products obtained by reacting an epoxy-containing monomer such as glycidyl methacrylate and an amine-oxide containing compound, such as hydroxyethyl-N,N-dimethylamineoxide, containing a group reactive with the epoxy group; and products obtained by reacting an isocyanate-containing monomer such as 2-isocyanate ethyl(meth)acrylate and an amine-oxide-containing compound, such as hydroxyethyl-N,N-dimethylamineoxide, containing a group reactive with the isocyanate group.
Examples of the monomer represented by formula (II) include amine-oxide-introduced products obtained by forming the oxide of the nitrogen atom of alkyl-, aryl- or alkylaryl-added compounds such as 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 3-methyl-5-vinylpyridine, 4-methyl-5-vinylpyridine, 6-methyl-5-vinylpyridine, 2-methyl-4-vinylpyridine, 3-methyl-4-vinylpyridine, 2-lauryl-5-vinylpyridine, 2-lauryl-4-vinylpyridine, 2-(t-butyl)-5-vinylpyridine or 2-(t-butyl)-4-vinylpyridine.
Examples of the monomer represented by formula (III) include amine-oxide-introduced products obtained by forming oxide of the nitrogen atom of 1-vinylimidazole, 2-methyl-1-vinylimidazole, 4-methyl-1-vinylimidazole, 5-methyl-1-vinylimidazole, 2-lauryl-1-vinylimidazole and 4-(t-butyl)-1-vinylimidazole.
Examples of the monomer represented by formula (IV) include amine-oxide-introduced products such as 4-vinylmorpholine, 2-methyl-4-vinylmorpholine, 4-arylmorpholine, 1-vinylpiperidine, 4-methyl-4-vinylpiperidine, 2-lauryl-1-vinylpiperazine and 4-methylpiperazinoethyl methacrylate.
Among them, monomers represented by formula (I) are most preferred, and a (meth)acryloyloxyalkylene compound in which R2 and R3each independently represents a C1-4 alkyl group in formula (I) is particularly preferred.
Nitrogen-containing Monomer
Examples of the nitrogen-containing monomer before oxide formation include monomers represented by the following formulae (VI) to (IX): 
wherein R1-R10, a, b, m, n, p, X and Y have the same meanings as defined in the above formulae (I) to (IV).
The amine-oxide-containing monomer may be replaced with a hydrophilic monomer other than the component (A) (component (C)) in an amount of 30 wt. % or less.
Hydrophilic Monomer (C)
Examples of the hydrophilic monomer include nonionic, anionic and cationic monomers and amphoteric monomers having both anionic and cationic properties in a single molecule.
Among them, specific examples of the nonionic monomer include (meth)acrylonitrile, N-cyclohexylmaleimide, N-phenylmaleimide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-(meth)acryloyl morpholine; monomers derived from a (meth)acrylic acid or (meth)acrylamide and a C2-4 alkylene oxide, such as hydroxyethyl (meth)acrylate, polyethylene glycol (meth)acrylate, methoxypoly(ethylene glycol/propylene glycol) mono(meth)acrylate, polyethylene glycol di(meth)acrylate or N-polyoxyalkylene (meth)acrylamide; and hydrophilic monomers such as (meth)acrylamide.
Specific examples of the anionic monomer include unsaturated carboxylic acid monomers such as (meth)acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid and crotonic acid; half esters of an unsaturated polybasic anhydride (e.g., succinic anhydride, phthalic anhydride) and a hydroxyl-containing (meth)acrylate such as hydroxyethyl (meth)acrylate; monomers containing a sulfonic acid group such as sulfoethyl (meth)acrylate and monomers containing a phosphoric acid group such as acid phosphoxyethyl (meth)acrylate.
The above-exemplified anionic unsaturated monomer can be used as an acid or after being partially or completely neutralized with a basic compound. It is also possible to provide the monomer for copolymerization as an acid, followed by partially or completely neutralizating with a basic compound. Examples of the basic compound for the neutralization include hydroxides of an alkali metal such as sodium hydroxide or potassium hydroxide; inorganic basic compounds such as aqueous ammonia; alkanolamines such as ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol and aminomercaptopropane diol; and basic amino acid compounds such as lysine, arginine and histidine.
Examples of the cationic monomer include those obtained by cationizing a tertiary-amino-containing monomer such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, p-dimethylaminomethylstyrene, p-dimethylaminoethylstyrene, p-diethylaminomethylstyrene or p-diethylaminoethylstyrene with a cationizing agent, for example, a halogenated alkyl such as methyl chloride, methyl bromide or methyl iodide, a dialkylsulfuric acid such as dimethylsulfuric acid, an epichlorohydrin-added tertiary amine mineral acid salt such as N-(3-chloro-2-hydroxypropyl)-N,N,N-trimethylammonium chloride, an inorganic salt such as hydrochloric acid, hydrobromic acid, sulfuric acid or phosphoric acid, or a carboxylic acid such as formic acid, acetic acid or propionic acid.
Examples of the amphoteric unsaturated monomer include amphoteric ion monomers obtained by making amphoteric a tertiary-amino-containing monomer, which is a precursor of the above-described cationic monomer, using a denaturant such as a monohalofatty acid salt, for example, potassium monochloroacetate, sodium monochloroacetate or potassium monobromopropionate, propiolactone, butyrolactone or propansultone.
The amine-oxide-containing polymer for use as component (a) in the present invention preferably is a copolymer having a weight-average molecular weight of 10,000 to 500,000, and is composed of 15 to 90 wt. % of an amine-oxide-containing unsaturated monomer (A) and 85 to 10 wt. % of a hydrophobic unsaturated monomer (B).
When the amount of the component (A) is smaller than 15 wt. %, the water solubility of the resulting copolymer is reduced, resulting in the problem that the copolymer is not easily washed away at the time of hair washing. Amounts greater than 90 wt. %, on the other hand, make the hair sticky. Amounts outside the above range are therefore not preferred.
Hydrophobic Monomer (B)
Examples of the hydrophobic monomer (B) include hydrophobic vinyl monomers such as C1-24 alkyl (meth)acrylates, styrene, p-methylstyrene, p-chlorostyrene, vinyl methyl ether, vinyl cyclohexyl ether, vinyl acetate, diethyl maleate and dibutyl maleate, glycidyl (meth)acrylate and fluoroalkyl esters of (meth)acrylic acid. Examples also include macromonomers such as radical- polymerizable unsaturated-group-containing silicone macromonomers.
Specific examples of the above-described C1-24 alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, secondary-butyl (meth)acrylate, tertiary-butyl (meth)acrylate, pentyl (meth)acrylate, secondary-pentyl (meth)acrylate, 1-ethylpropyl (meth)acrylate, 2-methylbutyl (meth)acrylate, isopentyl (meth)acrylate, tertiary-pentyl (meth)acrylate, 3-methylbutyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, 2-methylpentyl (meth)acrylate, 4-methylpentyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, 2-heptyl (meth)acrylate, 3-heptyl (meth)acrylate, octyl (meth)acrylate, 2-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, 3,3,5-trimethylhexyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, docosyl (meth)acrylate, tetracosyl (meth)acrylate, methylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, benzyl (meth)acrylate and phenetyl (meth)acrylate.
Among them, C1-24 alkyl (meth)acrylates represented by the following formula (V) are preferred. 
wherein R1 represents a hydrogen atom or a methyl group and R14 represents a C1-24 alkyl group.
The component (B) is preferably added in an amount of 10 to 85 wt. %. When the amount exceeds 85 wt. %, the copolymer film has deteriorated smoothness and transparency and moreover, becomes sparingly soluble in water so that it is not easily washed away at the time of hair washing. Amounts smaller than 10 wt. %, on the other hand, make the hair sticky. Amounts outside the above range are therefore not preferred.
Polymerization Process
An amine-oxide-containing resin can be obtained by polymerizing the above-described monomer components by known methods such as solution polymerization, bulk polymerization or suspension polymerization generally in the presence of a radical polymerization initiator. The solution polymerization method is particularly suitable. Examples of the solvent that can be used for polymerization include organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, ethyl acetate, propyl acetate or butyl acetate. These solvents may be used either singly or in combination. The solvent is preferably used in an amount needed to provide a polymer concentration of 10 to 65 wt. % in the resulting copolymer solution.
Examples of the radical polymerization initiator include azo compounds such as 2,2xe2x80x2-azobisisobutyronitrile (AIBN), 2,2xe2x80x2-azobis(2,4-dimethylvaleronitrile), 2,2xe2x80x2-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2xe2x80x2-azobisisobutyrate, 2,2xe2x80x2-azobis(2-methylbutyronitrile) or 1,1xe2x80x2-azobis(1-cyclohexanecarbonitrile) and peroxides such as benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide and lauroyl peroxide. The polymerization initiator may generally be added in an amount of 0.01 to 5 wt. % based on the total amount of components (A) to (C).
The polymerization is generally carried out at 30 to 120xc2x0 C., preferably 40 to 100xc2x0 C. for 1 to 20 hours in an inert gas atmosphere such as nitrogen or argon. It is a common practice to charge the entire amount of all the monomers at the beginning of the polymerization, but it is also possible to add these monomers in portions by kind and/or weight.
Oxide Formation
An amine-oxide-containing resin is obtained by adding an oxide forming agent to a resin solution obtained by the polymerization of monomer components at 20 to 100xc2x0 C. for 0.1 to 100 hours, preferably 1 to 50 hours.
An oxidizing agent such as peroxide or ozone is used as the oxide forming agent for the resulting precursor. Specific examples of the peroxide include hydrogen peroxide, ammonium persulfate, sodium persulfate, peracetic acid, metachloroperbenzoic acid, benzoyl peroxide and t-butyl hydroperoxide, however, hydrogen peroxide is ordinarily used. The oxide forming agent is used in a molar equivalent amount of from 0.2 to 3 times relative to the functional group which is able to form an oxide in the precursor polymer, with a molar equivalent amount of 0.5 to 2 times being more preferred. The remaining portion of peroxide can be used without treatment or after treating with a known method. Specific examples of such treatment include the addition of a reducing agent or a metal catalyst, ion exchange treatment and treatment with activated charcoal.
The resin solution thus obtained can be used as is. It can also be used after isolating an amine-oxide-containing resin in a known manner such as by precipitation or removal of solvent by distillation. The isolated amine-oxide-containing resin can be further purified as needed by reprecipitation, solvent washing, membrane separation or adsorption treatment.
The resin thus obtained generally has a weight-average molecular weight of 10,000 to 500,000. Weight-average molecular weights of less than 10,000 reduce the hair setting property. Those greater than 500,000, on the other hand, deteriorate compatibility with water or the like and increase the viscosity of the solution. This results in problems of working efficiency or coating properties. (b) Water-soluble high-molecular polymers
The water-soluble polymer of component (b) is selected from nonionic polymers (b1), cationic polymers (b2), anionic polymers (b3) and amphoteric polymers (b4), and has a weight average molecular weight of 5,000 to 500,000, preferably 10,000 to 100,000.
In the present invention, the term xe2x80x9cwater solubilityxe2x80x9d as used herein means as follows: when an aqueous solution obtained by stirring 1 part by weight of polymer selected from (b1) to (b4) and 99 parts by weight of a deionized water under heat at 60xc2x0 C. for two hours is uniform even after cooling and being allowed to stand for one day at room temperature; and has, in a 1 cmxc3x971 cm cell, a transmittance of 70% or greater at 655 nm, it is regarded to have water solubility.
(b1) Nonionic Polymers
The nonionic polymer is a polymer having as an essential component a repeating unit derived from an unsaturated monomer containing a pyrrolidone ring, caprolactam ring, amide group, N-alkyl-substituted amide group, polyether group, acetamide group or formamide group. Specific examples of the polymer containing a pyrrolidone ring include polyvinyl pyrrolidone such as xe2x80x9cLuviskol K-12, K-17, K-30, K-60, K-80 and K-90xe2x80x9d(each, trade name; product of BASF AG) and xe2x80x9cPVP K-15, K-30, K-60, K-90 and K-120xe2x80x9d (each, trade name; product of ISP, Inc.); vinyl pyrrolidone/vinyl acetate copolymers such as xe2x80x9cLuviskol VA28, VA37, VA55, VA64 and VA73xe2x80x9d (each, trade name; product of BASF AG), xe2x80x9cPVP/VA-735, PVP/VA-635, PVP/VA-535, PVP/VA-335, PVP/VA-235, S-630xe2x80x9d (each trade name, product of ISP, Inc.); and vinyl pyrrolidone/vinyl acetate/vinyl propionate copolymers such as xe2x80x9cRuviskol VAP343xe2x80x9d (trade name; product of BASF AG).
Specific examples of the polymer containing as an essential component a repeating unit derived from an amide-, N-alkyl-substituted-amide- or polyether-containing unsaturated monomer include radical homopolymers of an unsaturated monomer such as (meth)acrylamide, N-octyl (meth)acrylamide, hydroxyethyl (meth)acrylate, (meth)acrylic acid methoxypolyethylene glycol, (meth)acrylic acid methoxypolyethylene glycol.polypropylene glycol; and radical copolymers with a C1-24 alkyl (meth)acrylate, vinyl acetate or the like.
(b2) Cationic Polymers
Specific examples of the synthetic cationic polymer include N-vinyl pyrrolidone/quaternized dimethylaminoethyl methacrylate copolymers such as xe2x80x9cGafquat 755N, 755 and 734xe2x80x9d (each, trade name; product of ISP, Inc.) and xe2x80x9cRuviquat PQ11xe2x80x9d (trade name; product of BASF AG); N-vinyl pyrrolidone/dimethylaminoethyl methacrylate copolymers such as xe2x80x9cCopolymer 845, 937 and 958xe2x80x9d (each, trade name; product of ISP, Inc.); N-vinyl pyrrolidone/N-vinyl caprolactam/dimethylaminoethyl methacrylate copolymers such as xe2x80x9cGafix VC-713xe2x80x9d (trade name; product of ISP, Inc.); N-vinyl pyrrolidone/methacrylamidopropyl trimethylammonium chloride copolymer such as xe2x80x9cGafquat HS-100xe2x80x9d (trade name; product of ISP, Inc.); N-vinyl pyrrolidone/quaternized methylvinyl imidazolium copolymer such as xe2x80x9cLuviquat FC370, FC550, FC905 and HM-552xe2x80x9d (each, trade name; product of BASF AG.); dimethyldiallylammonium chloride polymers and dimethyldiallylammonium chloride/acrylamide copolymers such as xe2x80x9cMerquat 100 and 550xe2x80x9d (trade name; Calgon); and quaternized dialkylaminoalkylene methacrylate/alkyl (meth)acrylate copolymers as disclosed in JP-A-4-21623 or JP-A-5-310538.
Examples of the cationic polymer obtained by modifying a natural product include hydroxyethyl cellulose/dimethyldiallyl ammonium chloride copolymers such as xe2x80x9cCellquat H-100 and L200xe2x80x9d (each, trade name; product of National Starch Inc.); reaction products of hydroxyethyl cellulose with an epoxylated trimethyl ammonium compound such as xe2x80x9cCellquat SC-240, SC-240C and SC-230Mxe2x80x9d (each, trade name; product of National Starch Inc.), xe2x80x9cUcare Polymer JR-125, JR-400 and JR-30Mxe2x80x9d (each, trade name; product of Amerchol); Reoguard G (trade name; product of Lion Corp.) and xe2x80x9cCatinal HC and LCxe2x80x9d (trade name; product of Toho Chemical Industry Co.); and quaternized chitosan such as xe2x80x9cKytamer PCxe2x80x9d (trade name; product of Amerchol). (b3) Anionic polymers
Anionic polymers are polymers having an acid group such as a carboxyl or sulfonic acid group. Specific examples include methyl vinyl ether/maleic anhydride alkyl half ester copolymers such as xe2x80x9cGantrez ES-225, ES-425, A-425, V-225 and V-425xe2x80x9d (each, trade name; product of ISP, Inc.); vinyl acetate/crotonic acid/vinyl neodecanoate copolymers such as xe2x80x9cResin 28-131xe2x80x9d (trade name; National Starch Inc.) and xe2x80x9cLuviset CAxe2x80x9d (trade name; product of BASF AG); vinyl acetate/crotonic acid/vinyl neodecanoate copolymers such as xe2x80x9cResin 28-2930xe2x80x9d (trade name; product of National Starch Inc.); vinyl acetate/monobutyl maleate/isobornyl acrylate copolymers such as xe2x80x9cADVANTAGE CPxe2x80x9d (trade name; product of ISP, Inc.); (meth)acrylic acid/(meth)acrylic ester copolymers such as xe2x80x9cRuvimer 100Pxe2x80x9d (trade name; product of BASF AG) and xe2x80x9cDiaholdxe2x80x9d (trade name; Mitsubishi Chemical); acrylic acid/acrylamide derivative copolymers such as xe2x80x9cUltrahold Strong and Ultrahold 8xe2x80x9d (each, trade name; product of BASF AG), xe2x80x9cVersatile 42xe2x80x9d (trade name; product of National Starch Inc.) and xe2x80x9cPlus Size L53Pxe2x80x9d (trade name; product of GOO Chemical); polyvinyl pyrrolidone/(meth)acrylic acid/(meth)acrylic ester copolymers such as xe2x80x9cLuviflex VBM35xe2x80x9d (trade name; product of BASF AG); and diethylene glycol/cyclohexane dimethanol/dimethyl isophthalate/sulfonated dimethyl isophthlate condensates such as xe2x80x9cEastman AQ Polymerxe2x80x9d (Eastman Chemical).
From the viewpoint of water solubility, the anionic copolymer is preferably used after its acid group is partially or wholly neutralized with a basic compound. Examples of such a basic compound include hydroxide of an alkali metal such as sodium hydroxide and potassium hydroxide, inorganic basic compounds such as aqueous ammonia, alkanolamines such as ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol and aminomercaptopropanediol; and basic amino acid compounds such as lysine, arginine and histidine. Among them, 2-amino-2-methyl-1-propanol and potassium hydroxide are preferred from the viewpoint of water solubility.
(b4) Amphoteric Polymers
Amphoteric polymers are polymers each containing as an essential component a repeating unit derived from an unsaturated monomer which contains a betaine structural group such as a carboxybetaine group, sulfobetaine group or phosphobetaine group; or polymers each containing as essential components both a repeating unit derived from an unsaturated monomer which contains an anionic group such as a carboxyl group, sulfonic acid group or phosphoric acid group and a repeating unit derived from an unsaturated monomer which contains a quaternary ammonium salt or a tertiary amino group. Specific examples of the polymer containing as an essential component a repeating unit derived from a betaine-structural-group-containing unsaturated monomer include methacrylic carboxybetaine polymers, which are dimethylaminoethyl methacrylate/alkyl methacrylate copolymers modified with a monohaloacetate, for example, xe2x80x9cYukaformer 205A, SM, AMPHOSET, 201, R102, R402, 510, 201, W (each, trade name; product of Mitsubishi Chemical). This technology is disclosed in JP-A-51-9732, JP-A-55-104209, JP-A-61-258804 and JP-7-285832.
Examples of the polymer which comprises as essential components both a repeating unit derived from an unsaturated monomer containing an anionic group such as a carboxyl, sulfonic acid or phosphoric acid group and a repeating unit derived from an unsaturated monomer containing a quaternary ammonium salt or a tertiary amino group include hydroxypropyl acrylate/butylaminoethyl methacrylate/octylamide acrylate copolymers such as xe2x80x9cAmformer 28-4910, LV-71 and LV-47xe2x80x9d (each, trade name; product of National Starch Inc.), which are polymers each comprising as essential components both a repeating unit derived from a carboxyl-containing unsaturated monomer and a repeating unit derived from a tertiary-amino-containing unsaturated monomer; and diallyldimethylammonium chloride/acrylic acid copolymers such as xe2x80x9cMerquat 295xe2x80x9d (trade name; product of Calgon), and diallyldimethylammonium chloride/acrylic acid/acrylamide copolymers such as xe2x80x9cMerquat Plus 3330xe2x80x9d (trade name; product of Calgon), which are polymers comprising as essential components both a repeating unit derived from a carboxyl-containing unsaturated monomer and a repeating unit derived from a quaternary-ammonium-salt-containing unsaturated monomer.
Composition Ratio
In the hair cosmetic composition of the present invention, the weight ratio of the amine-oxide-containing copolymer of component (a) to the nonionic polymer of component (b1) falls within a range of from 1:10 to 10:1, preferably from 1:5 to 10:1. When the weight ratio is less than 1:10, the resulting composition has insufficient flexibility, makes the hair sticky, has insufficient hair setting effects and causes problems such as flaking when combed or difficulty in setting the hair into a desired shape due to static electricity. When the above ratio exceeds 10:1, the resulting composition cannot impart sufficient hardness so that the hair thus set lacks tautness and has a heavy finish feeling, resulting in deterioration of the touch feeling thus obtained. The total amount of components (a) and (b) in the hair cosmetic composition is 0.1 to 10 wt. %, preferably 0.5 to 8%, based on the total weight of the hair cosmetic composition. Amounts of less than 0.1 wt. % provide an insufficient hair setting property, while those exceeding 10 wt. % increase stiffness and deteriorate the touch feeling.
The weight ratio of the amine-oxide-containing copolymer of component (a) to the cationic polymer of component (b2) is within a range of from 1:10 to 10:1, with 1:5 to 10:1 being preferred. When the ratio of (a) to (b2) is less than 1:10, the hair setting effects are insufficient. This prevents the retention of a desired hair shape, and hair that is set with such a composition does not have sufficient resilience under high humidity conditions and becomes sticky. Moreover, repeated use of the composition over a long time period causes problems such as build-up. When the ratio exceeds 10:1, on the other hand, hair that is set with the resulting cosmetic composition cannot be easily combed due to lack of a sliding feeling, and moreover, the smoothness after drying is insufficient. The total amount of components (a) and (b2) is 0.1 to 10 wt. %, preferably 0.5 to 8 wt. %, based on the total amount of the hair cosmetic composition. Amounts of less than 0.1 wt. % lead to insufficient hair setting power, while those exceeding 10 wt. % increase stiffness and deteriorate the touch feeling.
The weight ratio of the amine-oxide-containing polymer of component (a) to the anionic polymer (b3) is 1:10 to 10:1, preferably 1:5 to 10:1. When the ratio is less than 1:10, the resulting cosmetic composition has insufficient flexibility, makes the hair stiff and provides insufficient hair setting effects. This leads to flaking upon combing, and difficulty in setting the hair to a desired shape due to static electricity. When the ratio exceeds 10:1, on the other hand, the resulting composition does not impart sufficient hardness so that the hair thus set lacks tautness and has a heavy (deteriorated) finish feeling. The total amount of components (a) and (b3) is 0.1 to 10 wt. %, preferably 0.5 to 8%, based on the total weight of the hair cosmetic composition. Amounts of less than 0.1 wt. % result in an insufficient hair setting property, while those exceeding 10 wt. % increase stiffness, to thereby deteriorate the feeling touch.
The weight ratio of the amine-oxide-containing polymer of component (a) to the amphoteric polymer (b4) is 1:10 to 10:1, preferably 1:5 to 10:1. When the ratio is less than 1:10, the resulting cosmetic composition has insufficient flexibility, makes the hair stiff, has insufficient hair setting effects to retain a desired shape under high humidity conditions, and is not adequately removed by hair washing. When the ratio exceeds 10:1, on the other hand, the resulting composition does not impart sufficient hardness so that the hair thus set lacks tautness and has a heavy finish feeling, resulting in deterioration of the touch feeling thus obtained. In addition, upon combing after setting the hair with the composition, flaking occurs in which the film thus formed is divided into small flakes. The total amount of components (a) and (b4) is 0.1 to 10 wt. %, preferably 0.5 to 8%, based on the total weight of the cosmetic composition. Amounts of less than 0.1 wt. % result in insufficient hair setting effects, while those exceeding 10 wt. % increase stiffness, to thereby deteriorate the touch feeling.
In the hair cosmetic composition, the amine-oxide-containing polymer (a) having a weight-average molecular weight of 10,000 to 500,000 is preferably used in an amount of 0.1 to 9 wt. %, with 0.1 to 5 wt. % being more preferred; and the water-soluble polymer (b) is preferably used in an amount of 0.1 to 9 wt. %, with 0.1 to 5 wt. % being more preferred.
The water-soluble polymers (b1), (b2), (b3) and (b4) of the component (b) can be used in combination insofar as the combination does not cause gelation. Examples of such combinations include (b1) and (b2); (b1), (b2) and (b4); (b1) and (b3); (b1) and (b4); (b2) and (b4); (b3) and (b4).
In addition to the above-described essential components (a) and (b), it is possible to incorporate into the cosmetic composition of the present invention the following components which are ordinarily used in cosmetic compositions to the extent of not impairing the advantages of the present invention. Examples thereof include glycerides such as castor oil, cacao oil, mink oil, avocado oil, jojoba oil, macadamia nut oil and olive oil; waxes such as beeswax and lanolin, hydrocarbons such as fluid paraffin, solid paraffin isoparaffin and squalane; linear or branched higher alcohols such as cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, lauryl alcohol and 2-octyl dodecanol; polyvalent alcohols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin and sorbitol; ethylene oxide and/or propylene oxide adducts of a higher alcohol such as polyoxyethylene lauryl ether, polyoxypropylene cetyl ether and polyoxyethylene polyoxypropylene stearyl ether; esters such as isopropyl myristate, octyldodecyl myristate, hexyl laurate and cetyl lactate; amides such as oleic diethanolamide and lauric diethanolamide; silicone derivatives such as dimethyl polysiloxane, methylphenyl polysiloxane, polyether-modified silicone and amino-modified silicone; cationic surfactants such as stearyl trimethylammonium chloride, distearyl dimethylammonium chloride and lauryl trimethylammonium chloride; anionic surfactants such as polyoxyethylene laurylether sulfate and polyoxyethylene lauryl sulfosuccinate salt; amphoteric surfactants such as lauryl hydroxysulfobetaine and lauryl dimethylcarboxybetaine; protein derivatives and amino acid derivatives such as collagen hydrolyzates, keratin hydrolyzates and polyamino acid; vegetable extracts, crude drugs, vitamins and ultraviolet absorbers such as oxybenzene, chelating agents such as EDTA-Na, antiseptics such as paraben, antioxidants, colorants, pigments and perfumes.
No particular limitation is imposed on the application or form of the hair cosmetic composition of the present invention. It can be used in the form of an aerosol hair spray, hair spray pump, hair spray foam, hair mist, setting lotion, hair gel, hair cream or hair oil.
The hair cosmetic composition of the present invention can be prepared by dissolving or dispersing its constituent components including the above-described components (a) and (b) in a solvent such as water and/or an alcohol such as ethanol or isopropanol in a manner well known to those of ordinary skill in the art. The hair cosmetic composition in each form can be prepared according to the following formulation.
Examples of the surfactant (c) for use in the shampoo or rinse include anionic surfactants such as N-(fatty acid acyl)-N-methyl-xcex2-alanine salts, e.g., N-cocoyl-N-methyl-xcex2alanine sodium and N-myristoyl-N-methyl-xcex2-alanine sodium; amphoteric surfactants such as cocoacidpropylbetaine, dimethyllaurylbetaine, bis(2-hydroxyethyl)laurylbetaine, cyclic laurylamine oxide, dimethyllaurylamine oxide and bis(2-hydroxyoxyl)laurylamine oxide; nonionic surfactants such as stearic diethanol amide, coconut oil fatty acid diethanol amide, sorbitan sesquioleate and polyoxyethylene stearyl ether; and cationic surfactants such as stearyltrimethylammonium chloride, distearyldimethylammonium chloride and stearyldimethylbenzylammonium chloride.
Examples of the nonionic surfactant (c) for use in the hair mousse include sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil and fatty acid alkanol amide.
Examples of the liquefied gas (d) for use in the hair mousse include liquefied petroleum gas, dimethyl ether, trichloromonofluoromethane and dichlorodifluoromethane. Examples of the propellant (g) for use in the hair spray include liquefied gases such as liquefied petroleum gas, dimethyl ether and halogenated hydrocarbon and compressed gases such as air, carbon dioxide gas and nitrogen gas.
As the water-soluble solvent (e), water, ethanol or isopropanol can be used, with water being mainly used.
Examples of the organic solvent having a boiling point of 50 to 300xc2x0 C. include hydrocarbon alcohols such as ethanol, isopropyl alcohol and ethylene glycol.
The present invention is hereinafter described in greater detail by reference to the following Examples. However, the present invention should not be construed as being limited thereto. All parts and percentages are given by weight unless otherwise indicated.